CN113430443A - Preparation method of superfine WC hard alloy - Google Patents
Preparation method of superfine WC hard alloy Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
The invention discloses a method for preparing superfine WC hard alloy with a molecular formula of WC-T-HAE, wherein T is at least one of carbide, oxide or boride, and HAE is high-entropy alloy; smelting and casting the raw material of the high-entropy alloy to prepare a high-entropy alloy ingot; under the protection of inert atmosphere, crushing the high-entropy alloy cast ingot by adopting a mechanical crushing mode to obtain high-entropy alloy coarse powder; adding submicron WC powder, T powder and the high-entropy alloy coarse powder into an airflow mill powder making machine according to the proportion of the components of the superfine WC hard alloy, performing airflow mill grinding in an inert atmosphere, removing the grading step, mixing the powder below 1 mu m separated originally into the ground powder to obtain mixed fine powder, and then performing press forming and sintering. The invention can solve the problem of overhigh oxygen content in the preparation process of the superfine WC hard alloy, improve the processing performance of the superfine WC hard alloy and meet the optical surface requirement through processing.
Description
Technical Field
The invention relates to a preparation method of WC-based hard alloy, in particular to a preparation method of ultrafine WC hard alloy without Co and Ni binding phase.
Background
Compared with the traditional WC-Co hard alloy, the hard alloy without the Co and Ni binding phase has higher hardness and elastic modulus, and meanwhile, the corrosion resistance and the wear resistance are also greatly improved, and the hard alloy is gradually applied to the fields of precision optical molds, sand blasting nozzles, nuclear industry sealing elements and the like which require high precision, high hardness, high elastic modulus and high corrosion resistance.
Chinese patent application CN1827817A discloses a high-entropy alloy binder and composite carbide sintered hard alloy and a manufacturing method thereof, wherein the composite carbide and metal powder of a binder phase are weighed and mixed in a ball milling cylinder, then the ball milling cylinder is put in a ball mill for high-energy ball milling for at least 10 hours, then 1-2 wt% of paraffin is added in the ball milling cylinder as a wetting agent and the binder, low-energy ball milling is carried out for at least 5 hours, discharging and drying are carried out, pressing is carried out to obtain a round blank, then degreasing and sintering are carried out, and finally a finished product is obtained.
The preparation method of the existing superfine WC hard alloy without Co and Ni binding phase comprises the steps of firstly preparing submicron WC powder by a high-energy ball milling method, improving the surface energy of the powder, and then preparing the superfine WC hard alloy without the binding phase by a discharge plasma sintering technology.
Disclosure of Invention
The invention aims to provide a preparation method of WC-based hard alloy, which can overcome the problem of overhigh oxygen content in the preparation process of superfine WC hard alloy, improve the processing performance of the superfine WC hard alloy and meet the optical surface requirement through processing.
The technical scheme provided by the invention is as follows:
a preparation method of superfine WC hard alloy is provided, wherein the molecular formula of the superfine WC hard alloy is WC-T-HAE, wherein T is at least one of carbide, oxide or boride, the T contains B element, and HAE is high-entropy alloy; the HAE is selected from at least five elements of Al, Nb, Ti, Zr, Ge, Si, V, Ta, Cr, Mn, Ce, Mo, W and Hf; the T contains B element, and the preparation method comprises the following steps:
step a, putting the raw material of the high-entropy alloy into a vacuum smelting furnace for smelting, and casting molten liquid obtained by smelting to obtain a high-entropy alloy ingot;
b, under the protection of inert atmosphere, crushing the high-entropy alloy cast ingot by adopting a mechanical crushing mode to obtain high-entropy alloy coarse powder;
c, adding submicron WC powder, T powder and the high-entropy alloy coarse powder into an airflow mill pulverizer according to the proportion of the components of the superfine WC hard alloy, performing airflow milling pulverization in an inert atmosphere, removing the classification step, and mixing the powder which is separated originally and is less than 1 micron into the pulverized powder to obtain mixed fine powder; the superfine WC hard alloy comprises the following components: 0.5 wt% to 5 wt% of HAE, less than 35 wt% of T, 0.1 wt% to 3 wt% of B, and the balance of WC and unavoidable impurities;
step d: and carrying out press forming and sintering on the mixed fine powder to obtain the superfine WC hard alloy.
According to the invention, the high-entropy alloy is added in the form of alloy powder, compared with the situation that each element of the high-entropy alloy is added in the form of metal simple substance powder, the oxidation of partial active elements of the high-entropy alloy can be effectively avoided, the reduction of oxygen content is facilitated, the low-oxygen preparation process is adopted, the condition that the submicron WC powder adsorbs oxygen in the preparation process can be avoided, the processing performance of the superfine WC hard alloy is improved, and after the processing, the surface roughness Ra of the superfine WC hard alloy is less than or equal to 10 nm.
On the other hand, the superfine WC hard alloy introduces high-entropy alloy and fully plays the role of B element, and HAE and B in an alloy system play a role in a synergistic way, so that the whole superfine WC hard alloy has excellent strength and toughness, higher thermal conductivity and thermal stability and high density, and can meet the requirements of an optical die: the thermal conductivity is more than or equal to 72W/m.K, and the density is more than or equal to 12 g.cm-3Hardness HRA is more than or equal to 70, and fracture toughness is more than or equal to 10 MPa.M1/2Bending strength is not less than 1600 N.mm-2Oxidation weight gain is less than or equal to 1.16mg cm-2And the surface roughness Ra is less than or equal to 10nm after processing.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a recommended embodiment, when the vacuum induction melting furnace is vacuumized to the vacuum degree of 4Pa-9Pa, argon gas is filled into the melting chamber to ensure that the pressure in the furnace is 0.03MPa-0.06MPa, and then melting is carried out.
In a recommended embodiment, the mechanical crushing is carried out by adopting two jaw crushers to be connected in series in a closed mode, and the high-entropy alloy ingot is crushed into 1mm-3mm coarse powder under the protection of inert atmosphere. The mechanical crushing method is not limited to a jaw crusher, and a combined mode of turning and high-speed crushing or other crushing modes can be adopted. The inert atmosphere may be an atmosphere containing an inert gas or nitrogen as is conventional in the art.
In a recommended embodiment, the pressure of the crushing chamber of the jet mill is 5MPa-11MPa, and the rotation speed of the sorting wheel is 3500rpm-4300 rpm.
In a preferred embodiment, the WC powder has an average particle size of 0.2 to 0.8 μm and the T powder has an average particle size of 0.5 to 1 μm.
In a preferred embodiment, the removing and classifying step is to add a filter communicated with a compressor of the jet mill pulverizer through a pipeline in a cyclone separator of the jet mill pulverizer, and the filter is set to block ultra-fine powder from passing through, so that powder with a particle size of less than 1 μm is not separated in the cyclone separator and mixed in the pulverized powder.
In a recommended embodiment, in the step d, the green body formed by pressing is placed in a spark plasma sintering furnace and vacuumized, the sintering pressure is adjusted to 35MPa-60MPa, the temperature is raised to 750-800 ℃, the temperature is kept for 1min-2min, the temperature is continuously raised to 1500-1700 ℃, and the temperature is kept for 5min-30 min.
In a preferred embodiment, the HAE has a melting point of 1850 ℃ or less.
In a preferred embodiment, T is Al4C3、HfC、TiC、Cr3C2、VC、ZrC、NbC、TaC、SiC、Mn3C、MoC、CuC、Mg2C3、W2C、CeO2、La2O3、MgO、ZrO2、Al2O3、ZrB2、CrB2、TiB2Or MnB2At least two of;
in a preferred embodiment, B is preferably present as a transition metal boride, such as ZrB2、CrB2、TiB2Or MnB2。
In a preferred embodiment, the high entropy alloy HAE is selected from the group consisting of alloys of formula Al0.4Hf0.6NbTaTiZr、AlMo0.5NbTa0.5TiZr、AlNbTaTiV、AlNb1.5Ta0.5Ti1.5Zr0.5、AlCr2Mo2Nb2Ti2Zr、HfMoNbTiZr、HfNbTaTiZr、HfNbTiVZr、CrNbTiVZr、CrMo0.5NbTa0.5At least one of TiZr, tizhfnbcr, TiNbMoTaW, TiVNbMoTaW, HfMoTaTiZr, or hfmonbtitzr. The inclusion of a metal element with a slightly larger atomic radius and the remaining elements with a closer atomic radius in the above formula is beneficial in HAE formation, where the metal element with a slightly larger atomic radius enters the crystal lattice and promotesThe crystal lattice is distorted, and the crystal lattice is transformed from a face-centered cubic phase to a body-centered cubic phase; during the sintering process, the selected elements are easy to combine among atoms to form ordered solid solution; meanwhile, the selected HAE is more beneficial to improving the thermal conductivity and the thermal stability of the WC-based hard alloy.
It is to be understood that all numerical ranges disclosed herein include all points within the range.
Evaluation procedure of oxygen content in sintered body: the oxygen content in the sintered body was measured by using an oxygen-nitrogen analyzer model EMGA-620W from HORIBA, Japan.
And (3) hardness testing: refer to GB/T7997-2014 Vickers hardness test method for hard alloy.
Bending strength and compressive strength: the measurement is carried out by adopting a CMT5305 microcomputer control universal testing machine, and reference is made to GB/T3851-2015 method for measuring transverse breaking strength of hard alloy and GB/T23370-2009 method for testing compression of hard alloy.
And (3) toughness testing: refer to GB/T33819 and 2017 Babbitt toughness test of hard alloy.
Thermal conductivity: adopts a German relaxation-resistant LFA457 type laser thermal conductivity instrument, and refers to the standard GB/T22588-2008.
Density: the American McCuPyc II 1340 true density analyzer.
Oxidation resistance: refer to GB/T13303 & 1991 method for measuring oxidation resistance of steel.
Surface roughness: the shape retention by shadow is adopted for measurement, refer to GB/T15056-.
The present invention will be described in further detail with reference to examples.
Example one
The preparation method of the superfine WC hard alloy comprises the following steps:
(1) vacuum melting
According to the molecular formula of high-entropy alloy HAE (Ha-alloy-oriented strand grains) AlNb1.5Ta0.5Ti1.5Zr0.5Preparing five kinds of metal simple substance powder (Al, Nb, Ta, Ti and Zr) for forming HAE, and putting the five kinds of metal simple substance powder into a vacuum chamberAnd (3) in the air induction smelting furnace, vacuumizing to 5Pa, filling argon into the smelting chamber to enable the pressure in the furnace to be 0.05MPa, and then smelting and pouring to obtain the high-entropy alloy ingot.
(2) Coarse crushing
Under the protection of inert atmosphere, two jaw crushers are adopted to be connected in series in a closed mode, and under the protection of high-purity nitrogen (99.99%), the high-entropy alloy cast ingot is crushed into coarse powder of 1-3 mm, and the high-entropy alloy coarse powder is obtained.
(3) Fine crushing and mixing
Adding WC powder with the average particle size of 0.8 mu m, WC powder with the average particle size of 0.5 mu m T and the high-entropy alloy coarse powder into a jet mill pulverizer according to the component proportion of the superfine WC hard alloy shown in the table 1, carrying out jet mill pulverization under the conditions that the pressure of a pulverizing chamber is 10MPa and the rotating speed of a sorting wheel is 3500rpm in a nitrogen atmosphere, additionally arranging a filter communicated with a compressor of the jet mill pulverizer through a pipeline in a cyclone separator of the jet mill pulverizer, and setting the filter to be capable of blocking the superfine powder from passing through, so that the powder with the particle size of less than 1 mu m is not separated out in the cyclone separator, and obtaining mixed fine powder.
(4) Pressing
And pressing the mixed fine powder under the pressure of 180MPa, and keeping the pressure for 120s to obtain a green body.
(5) Sintering
And placing the green body in a discharge plasma sintering furnace, vacuumizing, adjusting the sintering pressure to 50MPa, heating to 800 ℃, keeping the temperature for 1min, continuing heating to 1500 ℃, keeping the temperature for 10min, cooling to obtain the superfine WC hard alloy, and performing surface polishing treatment by adopting nano-grade diamond grinding paste.
TABLE 1 ingredient ratios of examples and comparative examples
The cemented carbides of the respective examples and comparative examples were subjected to performance tests, and the results are shown in table 2.
TABLE 2 measurement of the Properties of the examples and comparative examples
In the above examples 1-7, the ultra-fine WC-based cemented carbide components were combined with a low-oxygen preparation process, and the thermal conductivity of the alloy in each example was not less than 72W/m.K, and the density was not less than 12 g.cm-3Hardness is not less than 70, and fracture toughness is not less than 10 MPa.M1/2Bending strength is not less than 1600 N.mm-2Oxidation weight gain is less than or equal to 1.16mg cm-2The oxygen content of the alloy is less than 50ppm, and the surface roughness Ra of the polished hard alloy of each embodiment is less than or equal to 10nm, which all meet the requirements of alloy molds for manufacturing optical lenses.
In examples 1 to 7, when the amount of the HAE added is 0.5 wt% to 5 wt% and the amount of the B added is 0.1 wt% to 3 wt%, the amount of the HAE added is increased, the hardness and the bending strength of the alloy are reduced, the thermal conductivity and the fracture toughness are improved, and the oxidation weight gain is slightly increased, that is, the oxidation resistance is slightly reduced; and other elements such as Ta, Al and the like are added, so that the strength of the alloy can be properly enhanced, and the hardness and the bending strength are increased.
Comparative example 1 resulted in an alloy hardness of less than 70 and an oxidation weight gain of more than 1.16mg cm due to HAE of more than 5 wt%, compared to example 1-2The polished surface roughness Ra of the alloy prepared by the method is higher than 10nm, and obviously does not meet the requirement of an alloy mold for an optical lens.
Comparative example 2 has a fracture toughness of less than 10 MPa.M for alloys with B higher than 3 wt%, compared to example 41/2The oxidation weight gain is more than 1.16mg cm-2The polished surface roughness Ra of the alloy is higher than 10nm, which obviously does not meet the requirement of an alloy mold for an optical lens.
In comparative example 3, no HAE was added, resulting in an alloy fracture toughness of less than 10MPa M, compared to example 1 with 5 wt% HAE added1/2And the oxidation weight gain is obviously higher than 1.16mg cm-2The surface roughness Ra of the alloy after polishing is obviously higher than 10nm, which obviously does not meet the requirement of an alloy mould for an optical lens;
comparative example 4, without the addition of B, resulted in an alloy hardness of less than 70 and an oxidation weight gain of greater than 1.16mg cm, compared to example 1-2The surface roughness Ra of the polished alloy is higher than 10nm, and obviously the alloy does not meet the requirement of an alloy mold for an optical lens.
Example two
Examples 8-12 ultra-fine WC cemented carbides were prepared as in example 1 except that the HAE powder molecular formula composition in the raw materials was not identical, and the composition in the ultra-fine WC based cemented carbides is shown in table 3.
Table 3 HAE composition in cemented carbide of examples
| Serial number | HAE composition in cemented carbide |
| Example 8 | Al0.4Hf0.6NbTaTiZr |
| Example 9 | HfNbTaTiZr |
| Example 10 | TiVNbMoTaW |
| Example 11 | CrMo0.5NbTa0.5TiZr |
| Example 12 | AlCr2Mo2Nb2Ti2Zr |
The cemented carbide of each example was subjected to performance testing, and the results are shown in table 4.
Table 4 examples property measurements
In examples 8 to 12, the ultra-fine WC-based cemented carbide composition was combined with a low-oxygen preparation process, the oxygen content of the alloys of each example was less than 50ppm, and the thermal conductivity, density, hardness, fracture toughness, bending strength, and oxidation weight gain of each alloy met the requirements of an alloy mold for optical lenses: the thermal conductivity is more than or equal to 72W/m.K, and the density is more than or equal to 12 g.cm-3Hardness HRA is more than or equal to 70, and fracture toughness is more than or equal to 10 MPa.M1/2Bending strength is not less than 1600 N.mm-2Oxidation weight gain is less than or equal to 1.16mg cm-2。
Comparative example 1
The preparation method of the superfine WC hard alloy of the first comparative example comprises the following steps:
(1) raw material preparation
WC powder with an average particle size of 0.8 μm; five kinds of metal simple substance powder (Al, Nb, Ta, Ti and Zr) forming HAE have the grain diameter of 0.5 mu m; and ceramic powder T with a particle size of 0.5 μm and composed of boron carbide, titanium carbide, tantalum carbide or aluminum oxide.
TABLE 5 comparative example component ratios
(2) Ball mill
a. Carrying out high-energy ball milling on the elemental powder forming the HAE, wherein the ball-material ratio is 15:1, the rotating speed is 400r/min, the ball milling medium is hard alloy balls, and the time is 24h, so as to obtain HAE alloy powder;
b. adding WC powder and the ceramic powder T, and carrying out ball milling at a ball-to-material ratio of 5:1 and a rotation speed of 100r/min for 40 h.
(3) Pressing
Pressing under the pressure of 180MPa for 120s to obtain a green body.
(4) Sintering
And (3) placing the green body in a sintering furnace, performing discharge plasma sintering at 1600 ℃ and 60MPa sintering pressure for 30min under the condition that the vacuum degree is higher than 10Pa, and cooling to obtain the WC-based hard alloy.
The cemented carbides of the respective examples and comparative examples were subjected to performance tests, and the results are shown in table 6.
Table 6 comparative example performance measurements
Compared with the example 1, the comparative example 5 has the advantages that excessive oxygen is easily introduced due to no inert gas protection in the preparation process, a carbon-deficient phase is easily generated by reaction with free carbon in the sintering process, the oxygen content of the alloy is suddenly increased by over 100ppm, and the hardness, the oxidation weight gain and the surface roughness after processing of the final alloy do not meet the requirements of an optical lens mould;
compared with example 2, comparative example 6 is easy to introduce excessive oxygen due to the fact that the preparation process is not protected by inert gas, carbon-deficient phase is easy to react with free carbon in the sintering process, the oxygen content of the alloy is suddenly increased to exceed 100ppm, and the final oxidation weight gain and the surface roughness of the alloy do not meet the requirements of optical lens molds.
EXAMPLE III
The superfine WC-based hard alloy obtained in the examples 1, 4, 9, 10 and 12 and the comparative examples 1 to 6 is applied to a mold for processing polycarbonate optical glass, after the surface of the mold is coated with a film, the mold is used for press forming an optical lens after the film is coated, the optical lens is placed under 3 cm in front of a square hole in front of a light source, the optical lens is inspected by slightly inclining the lens, the light source adopts a 20W fluorescent lamp or a 100W bulb, and the non-reflective object which is black before, above, below, left and right in the detection environment is required to be inspected, and a magnifying lens (4 times) is used for inspecting the flaws below #60 or # 60:
the optical glass manufactured by the mold made of the superfine WC hard alloy materials of the embodiments 1, 4, 9, 10 and 12 has good appearance;
the optical lenses manufactured by the molds made of the materials of the comparative examples 1 to 6 had poor appearance points and were not qualified.
The above examples are only intended to further illustrate some specific embodiments of the present invention, but the present invention is not limited to the examples, and any simple modification, equivalent change and modification made to the above examples according to the technical spirit of the present invention fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the superfine WC hard alloy is characterized in that the molecular formula of the superfine WC hard alloy is WC-T-HAE, wherein T is at least one of carbide, oxide or boride, the T contains B element, and HAE is high-entropy alloy; the HAE is selected from at least five elements of Al, Nb, Ti, Zr, Ge, Si, V, Ta, Cr, Mn, Ce, Mo, W and Hf; the T contains B element, and the preparation method comprises the following steps:
step a, putting the raw material of the high-entropy alloy into a vacuum smelting furnace for smelting, and casting molten liquid obtained by smelting to obtain a high-entropy alloy ingot;
b, under the protection of inert atmosphere, crushing the high-entropy alloy cast ingot by adopting a mechanical crushing mode to obtain high-entropy alloy coarse powder;
c, adding submicron WC powder, T powder and the high-entropy alloy coarse powder into an airflow mill pulverizer according to the proportion of the components of the superfine WC hard alloy, performing airflow milling pulverization in an inert atmosphere, removing the classification step, and mixing the powder which is separated originally and is less than 1 micron into the pulverized powder to obtain mixed fine powder; the superfine WC hard alloy comprises the following components: 0.5 wt% to 5 wt% of HAE, less than 35 wt% of T, 0.1 wt% to 3 wt% of B, and the balance of WC and unavoidable impurities; step d: and carrying out press forming and sintering on the mixed fine powder to obtain the superfine WC hard alloy.
2. The method for preparing the ultrafine WC hard alloy as recited in claim 1, wherein in the step a, when the vacuum induction melting furnace is evacuated to a vacuum degree of 4Pa to 9Pa, argon gas is introduced into the melting chamber to make the pressure in the furnace reach 0.03MPa to 0.06MPa, and then the melting is performed.
3. The method for preparing the ultrafine WC hard alloy according to claim 1, wherein in step b, the mechanical crushing is carried out by adopting two jaw crushers to close and serially connect, and the high-entropy alloy ingot is crushed into 1mm-3mm coarse powder under the protection of inert atmosphere.
4. The method for preparing the superfine WC hard alloy as recited in claim 1, wherein in step c, the pressure in the crushing chamber of the jet mill powder making machine is 5MPa-11MPa, and the rotation speed of the sorting wheel is 3500rpm-4300 rpm.
5. The method for preparing an ultra fine WC hard alloy in accordance with claim 1, wherein in step c, the submicron WC powder has an average particle size of 0.2 μm to 0.8 μm, and the T powder has an average particle size of 0.5 μm to 1 μm.
6. The method for preparing an ultrafine WC hard alloy as recited in claim 5, wherein in step c, the removing and classifying step is carried out by adding a filter connected to a compressor of the jet mill through a pipe to a cyclone of the jet mill, and setting the filter to block the ultrafine powder from passing through so that powder of less than 1 μm is not separated in the cyclone and mixed in the pulverized powder.
7. The method for preparing the superfine WC hard alloy as recited in claim 1, wherein in the step d, the pressed and formed blank is placed in a spark plasma sintering furnace and vacuumized, the sintering pressure is adjusted to 35MPa-60MPa, the temperature is increased to 750-.
8. The method of preparing an ultra-fine WC hard alloy as in claim 1, wherein the HAE has a melting point of 1850 ℃ or less.
9. The method of preparing an ultra-fine WC cemented carbide according to claim 1, wherein T is Al4C3、HfC、TiC、Cr3C2、VC、ZrC、NbC、TaC、SiC、Mn3C、MoC、CuC、Mg2C3、W2C、CeO2、La2O3、MgO、ZrO2、Al2O3、ZrB2、CrB2、TiB2Or MnB2At least two of; the B is present in the form of a transition metal boride.
10. The method for preparing the ultrafine WC hard alloy according to claim 1, wherein the high-entropy alloy HAE is selected from the group consisting of alloys with a molecular formula of Al0.4Hf0.6NbTaTiZr、AlMo0.5NbTa0.5TiZr、AlNbTaTiV、AlNb1.5Ta0.5Ti1.5Zr0.5、AlCr2Mo2Nb2Ti2Zr、HfMoNbTiZr、HfNbTaTiZr、HfNbTiVZr、CrNbTiVZr、CrMo0.5NbTa0.5At least one of TiZr, tizhfnbcr, TiNbMoTaW, TiVNbMoTaW, HfMoTaTiZr, or hfmonbtitzr.
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| TW111107197A TWI790133B (en) | 2021-06-18 | 2022-02-25 | Preparation method of superfine wc-base hard alloy |
| PCT/CN2022/088958 WO2022262421A1 (en) | 2021-06-18 | 2022-04-25 | Method for preparing ultrafine wc cemented carbide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115433011A (en) * | 2022-10-10 | 2022-12-06 | 北方民族大学 | High-entropy carbide (VNbTaMoW) C 5 -SiC complex phase ceramics |
| WO2022262421A1 (en) * | 2021-06-18 | 2022-12-22 | 厦门钨业股份有限公司 | Method for preparing ultrafine wc cemented carbide |
| WO2022262420A1 (en) * | 2021-06-18 | 2022-12-22 | 厦门钨业股份有限公司 | Wc-based hard alloy and application thereof |
| CN115627402A (en) * | 2022-07-14 | 2023-01-20 | 河源正信硬质合金有限公司 | Complex-phase co-strengthening hard alloy and preparation method thereof |
| CN115846668A (en) * | 2022-11-04 | 2023-03-28 | 安徽尚欣晶工新材料科技有限公司 | Hard alloy material for optical die and preparation method thereof |
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| CN116159999A (en) * | 2023-02-16 | 2023-05-26 | 成都美奢锐新材料有限公司 | Raw material powder, and material and mold for high-temperature oxidation environment prepared from raw material powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827817A (en) * | 2006-04-14 | 2006-09-06 | 韶关学院 | Hard alloy sintered by high-entropy alloy binder and compound carbide and preparation method thereof |
| CN102560215A (en) * | 2012-02-17 | 2012-07-11 | 中南大学 | Ni3Al bonded ultra-fine grained tungsten carbide-based hard alloy and preparation method thereof |
| KR20190135318A (en) * | 2018-05-28 | 2019-12-06 | 부산대학교 산학협력단 | Method for welding high entropy alloy containing chromium as active ingredient |
| CN111940723A (en) * | 2020-08-30 | 2020-11-17 | 中南大学 | Nano ceramic metal composite powder for 3D printing and application |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108060322B (en) * | 2017-12-07 | 2020-04-24 | 中南大学 | Preparation method of hard high-entropy alloy composite material |
| CN108823478B (en) * | 2018-06-14 | 2020-04-14 | 湖南金锐美新材料有限公司 | Ultra-fine high-entropy alloy binding phase metal ceramic and preparation method thereof |
| CN109252081B (en) * | 2018-10-31 | 2020-09-22 | 华南理工大学 | High-entropy alloy binding phase superfine tungsten carbide hard alloy and preparation method thereof |
| CN111235453B (en) * | 2020-03-23 | 2021-06-15 | 郑州轻工业大学 | Hard alloy with high-entropy alloy layer on surface and preparation method thereof |
| CN111961940B (en) * | 2020-08-20 | 2021-09-21 | 四川轻化工大学 | WC-based hard alloy containing high-entropy ceramic phase and preparation method thereof |
| CN113430443B (en) * | 2021-06-18 | 2022-06-10 | 厦门钨业股份有限公司 | Preparation method of superfine WC hard alloy |
| CN113462947B (en) * | 2021-06-18 | 2022-06-03 | 厦门钨业股份有限公司 | WC-based hard alloy and application thereof |
-
2021
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-
2022
- 2022-02-25 TW TW111107197A patent/TWI790133B/en active
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- 2022-04-25 WO PCT/CN2022/088958 patent/WO2022262421A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827817A (en) * | 2006-04-14 | 2006-09-06 | 韶关学院 | Hard alloy sintered by high-entropy alloy binder and compound carbide and preparation method thereof |
| CN102560215A (en) * | 2012-02-17 | 2012-07-11 | 中南大学 | Ni3Al bonded ultra-fine grained tungsten carbide-based hard alloy and preparation method thereof |
| KR20190135318A (en) * | 2018-05-28 | 2019-12-06 | 부산대학교 산학협력단 | Method for welding high entropy alloy containing chromium as active ingredient |
| CN111940723A (en) * | 2020-08-30 | 2020-11-17 | 中南大学 | Nano ceramic metal composite powder for 3D printing and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022262421A1 (en) * | 2021-06-18 | 2022-12-22 | 厦门钨业股份有限公司 | Method for preparing ultrafine wc cemented carbide |
| WO2022262420A1 (en) * | 2021-06-18 | 2022-12-22 | 厦门钨业股份有限公司 | Wc-based hard alloy and application thereof |
| CN115627402A (en) * | 2022-07-14 | 2023-01-20 | 河源正信硬质合金有限公司 | Complex-phase co-strengthening hard alloy and preparation method thereof |
| CN115433011A (en) * | 2022-10-10 | 2022-12-06 | 北方民族大学 | High-entropy carbide (VNbTaMoW) C 5 -SiC complex phase ceramics |
| CN115433011B (en) * | 2022-10-10 | 2023-08-18 | 北方民族大学 | High entropy carbide (VNbTaMoW) C 5 -SiC complex phase ceramics |
| CN115846668A (en) * | 2022-11-04 | 2023-03-28 | 安徽尚欣晶工新材料科技有限公司 | Hard alloy material for optical die and preparation method thereof |
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| KR20230051574A (en) | 2023-04-18 |
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| CN113430443B (en) | 2022-06-10 |
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